Processes of synthesizing azo compounds

ABSTRACT

A method for preparing compounds of the formula:   WHEREIN: A is an alkyl radical of at least nine carbon atoms D is a monoazo, disazo or anthraquinone dye moiety; X is alkyl, alkoxy, hydroxy, amino, chloro or carboxy; and M IS AN INTEGER FROM 1-5. The compounds are useful in photographic processes for preparing colored images.

Uted States Patent [191 Huyfier Dec.9, 1975 PROCESSES OF SYNTHESIZIING AZO COMPOUNDS [75] Inventor: Paul S. Huyffer, Lynnfield, Mass.

[73] Assignee: Polaroid Corporation, Cambridge,

Mass.

22 Filed: Mar. 30, 1970 21 Appl. No.: 22,114

Related US. Application Data [63] Continuation of Ser. No. 655,306, July 24, 1967,

abandoned.

[52] US. Cl. 260/147; 260/162; 260/174; 260/197; 260/202; 260/372; 260/373;

[51] Int. C1. C07C 107/04 [58] Field of Search 260/147, 162, 202, 197

[56] References Cited UNITED STATES PATENTS 2,597,676 5/1952 Schetty 260/197 X Primary ExaminerF1oyd D. Higel Assistant Exa'miner-C. F. Warren Attorney, Agent, or Firm-John P. Morley [57] ABSTRACT A method for preparing compounds of the formula:

wherein:

A is an alkyl radical of at least nine carbon atoms D is a monoazo, disazo or anthraquinone .dye

moiety;

X is alkyl, alkoxy, hydroxy, amino, chloro or carboxy; and

m is an integer from 1-5. The compounds are useful in photographic processes for preparing colored images.

5 Claims, No Drawings This application is a continuation of Ser. No. 655,306, filed July 24, 1967, and now abandoned.

BACKGROUND OF INVENTION have an anchoring moiety which renders the com- 25 pound immobile and non-diffusible in a photographic processing composition. Upon oxidation, these compounds may autoreact intramolecularly in such a way as to form a new heterocyclic ring and, as a function of such reaction, to split off the dye moiety as a mobile 30 and diffusible color-providing material.

One group of compounds of this description are rep- 4 R (Il -l) OCH (II) NH l OCH (III) n-1 -NO l OCH 4 Lm R -HQ resented in this copending application as being of the formula:

wherein:

each of R and R comprises a long chain amide, e.g., of at least 13 carbon atoms, bonded directly to a nuclear carbon atom or linked indirectly thereto through an alkylene or phenylene substituent;.

D represents a dye moiety, e.g., a monoazo, disazo or anthraquinone dye moiety; and

n and 11 may be 1 or 2, provided that at least one of them is 2 to provide an anchoring moiety; and nuclear substituted derivatives thereof, e.g., where any of the nuclear carbon atoms of the respective benzene moieties not containing one of the specifically designated substituents may contain a carboxy, alkyl, alkoxy, amino, chloro, hydroxy or amide substituent.

Such compounds may be prepared by the following sequence of reactions:

OCH

[H NH The aforementioned compounds are of particular use in the photographic systems for preparing color images I which are described and claimed in the copending applicationsof Stanley M. Bloom and Howard G. Rogers,

Ser. No. 655,440, now US. Pat. No. 3,443,940; Stanley M. Bloom and Robert K. Stephens, Ser. No. 655,501 filed July 24, 1967 now abandoned in favor of application Ser. No. 789,837 filed Jan. 8, 1969, now US. Pat. No. 3,498,785 issued Mar. 3, 1970 and Stanley M. Bloom and Robert K. Stephens, Ser. No. 655,436, filed July 24, 1967 now US. Pat. No. 3,498,785 issued Mar. 3, 1970, all filed concurrently.

The present invention is directed to novel procedures for preparing compounds of the foregoing description, which procedures greatly facilitate synthesis of the desired compound and in fact make it possible to obtain readily certain compounds of the above-mentioned formula which can only be obtained with great difficulty, if at all.

SUM-MARY According to the present invention, compounds within the above-mentioned formula may be readily obtained by employing a methoxymethoxy substituent in lieu of a methoxy substituent as the protected hydroxy group in the above sequence of steps. The desired hydroxy group may be readily obtained by hydrolysis, e.g., with a mineral acid such as l-lCl.

The novel procedures of this invention may be employed in conjunction with the procedures described and claimed in the copending application of Harris L. Curtis, Ser. No. 655,304, filed July 24, 1967 now aban- X (m-l) l OCH OCH cloned in favor of US. Pat. application Ser. No. 20,482 filed Mar. 26, 1970 filed concurrently and directed to a novel synthesis of certain compounds within the scope of the above formula.

As was mentioned previously, this invention relates to novel procedures for preparing compounds useful in photographic processes for preparing color images.

A primary object of this invention, therefore, is to .provide novel procedures of the foregoing description.

Another object is to provide novel intermediates which may be readily hydrolyzed to obtain compounds containing a dye moiety and which also have an anchoring moiety rendering the compound immobile and non-diffusible in a photographic processing composition, which compounds, upon oxidation, may autoreact intramolecularly in such a way as to form a new heterocyclic ring and, as a function of such reaction, split off the dye moiety as a mobile and diffusible dye.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description.

The novel process of this invention by which the aforementioned objectives are accomplished may be illustrated by the following sequence of steps:

X (m-l) l OCH OCH In the above sequence of reactions, R, n and D have the meanings heretofore noted, X is an alkyl radical, e.g., methyl, an alkoxy radical, e.g., methoxy, hydroxy, amino, chloro, or carboxy; and m is a positive integer from 1-5 inclusive, it being understood that where m is 1, hydrogen atoms are bonded to the respective four unsubstituted carbon atoms.

The process of this invention may be employed in conjunction with the procedures described and claimed in the aforementioned application of Harris L. Curtis, Ser. No. 655,304 filed July 24, 1967 now abandoned in favor of US. patent application Ser. No.'20,482 filed Mar. 26, 1970 to prepare certain compounds within the scope of formula B, which compounds may be represented by the formula:

wherein D, X and m have the meanings heretofore The synthesis of compounds within the scope of fornoted, and mula (C) may be illustrated as follows:

A is an alkyl radical of at least nine carbon atoms.

T)CH OCH I C=O l A \OCH OCH 1 NH I IOCH OCH (III) 1 l m 3 X Y c 0 H S c 1 D c 02 S 2 H "Hr m c N 0 w 0 2 O w H H m m m C A Oil IN .lNiG A D D. m V m I X l X The starting p-methoxymethoxy-anilines of step I in the above two sets of reaction sequences are in general known in the art. They may be prepared by replacing the hydrogen atom of the hydroxyl moiety of the corresponding p-nitrophenol with a CH OCI-I substituent in known manner, e.g., methoxymethylation by reaction of the nitrophenol with ClCI-I OCH followed by catalytic hydrogenation to reduce the nitro group to an amino group to provide the desired methoxymethoxy compound. P-nitrophenols from which the starting protected derivative (methoxymethoxy derivative) may be obtained may be selected from those heretofore known in the art, e.g., p-nitrophenol, 4-nitro-2-methylphenol, 4-nitro-2-methoxyphenol, 4-nitro-2 carboxyphenol, 4-nitro-2-chlorophenol, 4-nitro-2,6-dimethylphenol, 4-nitro-2,6-dimethoxyphenol, 4,6-dinitro-2-methylphenol, 4-nitro-2-ethoxyphenol, 4-nitro-2-propoxyphenol, 4-nitro-2-butoxyphenol, 4-nitro-2amylphenol, 4-nitro-3-methylphenol, 4-nitro-3ethylphenol, 4-nitro- 3-penta-decylphenol, 4-nitro-3-decylphenol, 4-nitro- 2,6-dichlorophenol, 4-nitro-2-methoxy-6-methylphenol, 4-nitro-2-ethoxy-6-methyl-phenol, 4-nitro-2- methyl-o'propylphenol, 4-nitro-2,3-dimethylphenol, 4-nitro-3,5-dimethyl-phenol, 4-nitro-3-methyl-5-propyl-phenol, 4-nitro-2,S-dimethylphenol, 4-nitro-2-isopropyl-S-methylphenol, 4-nitro-2,5-dimethyoxyphenol etc.

The reduction of step II (as well as the aforementioned reduction of the nitro group following methoxymethylation) may be performed by hydrogenation in the presence of a catalyst, i.e., introducing hydrogen gas into a mixture containing the nitro compound and one of the known hydrogenation catalysts, e.g., Pd/BaSO Raney nickel, etc.

The dye sulfonyl chloride may be a sulfonyl chloride of any of the monoazo, disazo or anthraquinone dyes heretofore known in the art and may comprise any of the dye moieties disclosed in the aforementioned application Ser. No. 655,338 filed July 24, 1967, now US. Pat. Nos. 3,751,406. In general, dyes containing a sulfonyl chloride substituent making them useful in the practice of this invention are well known. Accordingly, a long list of useful dyes which may be employed will be readily suggested to those skilled in the art. The preparation of such dyes is described in numerous texts and therefore will also be apparent to those skilled in the art. (See, for example, Synthetic Dyes by Venkataraman, 1952, Vol. I, pp. 197-201).

The removal of the methoxymethyl protective group to form the desired hydroxy substituent may be readily accomplished by hydrolysis, e.g., with a mineral acid such as HCl in a suitable organic solvent such as methanol, ethanol, methyl cellosolve, etc.

The various reaction conditions, e.g., time, temperature and pressure of reaction, selection of solvents to form the reaction mixture, etc., are not essential to the practice of this invention and will be readily apparent to those skilled in the art in the light of the foregoing description. The essence of the invention is, therefore, the aforementioned selection of steps, in the order described, to obtain the desired dyes.

Where the dye employed is a. metal-complexable dye, e.g., an azo dye having chelatable groups such as hydroxy or carboxy groups ortho, ortho to the azo-linkage, the present invention is adaptable to the preparation of metal complexes of dyes within formula (B), e.g., chromium, nickel, copper, etc., complexes. The dye may be metal-complexed either before or after removal of the protected group to form the corresponding hydroxy analogue. For example, the chromium complex of a dye of formula (B) may be formed by reaction between a suitable chromium salt, e.g., chromium chloride and the methoxymethoxy analogue of a complexable dye of formula (B), in known manner for formation of chromium complexes, followed by hydrolysis to form the desired compound.

As examples of compounds within the scope of formula (B) which may be prepared by the present invention, mention may be made of the following:

I NH

-- N-==--N-U- COOH The following Examples show by way of illustration and not by way.of limitation the practice of this invention.

EXAMPLE 1 Fifteen grams of 4-fluoro-5-nitro-aniline, 35.0 g. of

stearoyl chloride and 8.4 g. of sodium bicarbonate were stirred overnight at room temperature. The reaction mixture was then refluxed and the insoluble inorganic salts were filtered off. Upon cooling of the filtrate, 2- fluoro-S-stearamido-nitrobenzene, an off-white solid was obtained, m.p. 8283 C., of the formula:

ll CH (CH2) C.-NH

8.0 g. of the above compound, 14.5 g. of p-methoxymethoxyganiline, 4.0 g. of magnesium oxide and 100.0 ml. of water were heated in a bomb with shaking at 180 C.

for 2 days. After cooling, the contents were filtered and the solid obtained thereby was recrystallized from ethyl. acetate to yield 6.0 g. of an orange cry'st m.p. l 181 19 C. of the formula:

alline solid,

l-p henyl-3-methyl-4-( 4 -chlorosulfonyl-2 '-acetoxynaphthalene-l )azopyrazolone-S-one in 100 ml. of pyridine were heated overnight on a steam bath. The mixture was then poured into 300.0 ml. of sodium bicarbonate and about 50.0 g. of ice. The resulting red solid was filtered and recrystallized form methanol to yield 5.0 g. of a sulfonamide, m.p. l39l4l C. of the formula:

The above compound may be hydrolyzed by stirring in hot 10%hydrochloric acid and then filtering to yield the compound of formula 1.

EXAMPLE 2 5.0 g. of the methoxymethoxy analogue of the compound of formula 1 (prepared as in Example 1) and 3.0 g. of chromium chloride were refluxed overnight in 100 ml. of ethanol. The solvent was removed in vacuo and the residue was then dissolved in hot chloroform and filtered. The chloroform was evaporated and the resulting magenta solid was stirred in hot 10% HC] and filtered to yield 3.0 g. of the chromium complex of formula 2.

By way of recapitulation, the present ivention is directed to a novel synthesis of a class of compounds described and claimed in the aforementioned application Ser. No. 655,338, filed July 24, 1967, now US. Pat. No. 3,751,406, which compounds are of particular use in color photography. In the preparation of these compounds it is necessary that the phenolic hydroxy group be protected during synthesis. The desired compound is finally obtained by removal of the protective groups.

In the aforementioned application Ser. No. (Case No. 341 l the phenolic hydroxy group is protected by methylation. Subsequent removal of the protective group to form the corresponding hydroxy analogue requires strong reaction conditions, e.g., by reaction with boron tribromide, which in many instances make it extremely difficult, if not impossible, to prepare certain compounds within the claimed class. These strong reaction conditions at times result in unwanted substitution of other desired moieties of the molecule and may even result in cleavage of the compound, thereby precluding formation of the desired compound.

By the present invention, these difficulties in synthesis are completely obviated by employing a methoxymethoxy substituent as the protective group in lieu of a methoxy substituent. The methoxymethoxy substituent, it has been discovered, may be readily removed by hydrolysis under mild conditions, e.g. with a mineral acid which do not result in any adverse side reactions.

Since certain changes may be made in the above product and process without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

,1. A process which comprises the steps of:

a. reacting a compound of the formula:

OCH OCH with a compound of the formula:

waQ

to form a compound of the formula:

OCH OCH OCH OCH NH l I c'. reacting said last-named compound with a dye salt of the formula:

Cl SO D to form a compound of the formula:

OCH OCH an-1) i? NH 6* NH- so D and d. removing said --Cl-l OCH group to form a compound of the formula:

m is a positive integer from 1 to 2;

A is an alkyl radical having from 9-17 carbon atoms;

and

D is an azo dye moiety.

2. A process as defined in claim 1 wherein said step (b) is effected by introducing hydrogen gas into a mixture comprising the nitro group to be reduced and a hydrogenation catalyst.

- 3. A process as defined in claim 1 wherein said Cl-l- OCH group is removed in step (d) by hydrolysis with hydrochloric acid.

4. A method of claim 1 which comprises reacting 2- fluoro-S-stearamido-nitrobenzene with p-methoxymethoXy aniline to form:

OCH ocH (CH2)16 CH3 hydrogenating said last-named compound to reduce the nitro group thereof to a primary amino group; and reacting the thus-formed amine with l-phenyl-3-methyl-4-(4-chl0rosulfonyl-2-acetoxy-naphthalenel')azopyrazolone-S-one to form:

OCH OCH l 2 3 l I NH N'HSO U I 3 OH HO T C O (cH CH and hydrolyzing said last-named compound to form a compound of the formula:

NH C? NHSO IFH v c o (cn l 

1. A PROCESS WHICH COMPRISES THE STEPS OF: A. REACTING A COMPOUND OF THE FORMULA:
 2. A process as defined in claim 1 wherein said step (b) is effected by introducing hydrogen gas into a mixture comprising the nitro group to be reduced and a hydrogenation catalyst.
 3. A process as defined in claim 1 wherein said -CH2OCH3 group is removed in step (d) by hydrolysis with hydrochloric acid.
 4. A method of claim 1 which comprises reacting 2-fluoro-5-stearamido-nitrobenzene with p-methoxymethoxy aniline to form:
 5. A process as defined in claim 4 including the steps of reacting said last-named compound with a chromoum salt to form the chromium complex of said compound; and hydrolyzing said last-named compound to form a compound of the formula: 